BIOACTIVE ADDITIVE FOR A FUEL, USES THEREOF, FUEL COMPOSITION, AND METHOD
20240279562 ยท 2024-08-22
Inventors
- Christoph HOCHSTEIN (Wolfratshausen, DE)
- Sabine RIHA (Gmund am Tegernsee, DE)
- Volker KN?THIG (Weilheim, DE)
Cpc classification
International classification
Abstract
The present disclosure relates to a bioactive additive, to the use thereof and to a fuel composition containing the additive, as well as to methods in which the additive or the fuel composition are used. The additive comprises at least one compound represented by the general formula (I) given below, wherein R is a saturated or unsaturated hydrocarbon residue having 14 to 20 carbon atoms; and n is an integer of 1 to 6.
##STR00001##
Claims
1.-15. (canceled)
16. A bioactive additive for a fuel, wherein the additive comprises at least one compound represented by the general formula (I) given below: ##STR00005## wherein R is a saturated or unsaturated hydrocarbon residue having 14 to 20 carbon atoms; and n is an integer from 1 to 6.
17. The additive according to claim 16, wherein R is a saturated or unsaturated hydrocarbon residue having 16 to 18 carbon atoms and n is an integer of 2 to 4.
18. The additive according to claim 16, wherein the additive further comprises at least one antioxidant.
19. The additive according to claim 16, wherein the additive further comprises at least one agent for increasing the ignitability.
20. The additive according to claim 16, wherein the additive further comprises at least one solvent.
21. The additive according to claim 16, wherein the additive comprises at least 50% by weight of the at least one compound of the general formula (I) and further comprises at least one of the following components: 5 to 20% by weight of at least one antioxidant; 5 to 20% by weight of at least one agent for increasing the ignitability; 5 to 30% by weight of at least one solvent.
22. A method for reducing microbial load and/or for stabilization of a fuel, the method comprising: adding an additive to a fuel, wherein the additive comprises at least one compound represented by the general formula (I) given below: ##STR00006## wherein R is a saturated or unsaturated hydrocarbon residue having 14 to 20 carbon atoms; and n is an integer from 1 to 6.
23. A fuel composition comprising a fuel and an additive, wherein the additive comprises at least one compound represented by the general formula (I) given below: ##STR00007## wherein R is a saturated or unsaturated hydrocarbon residue having 14 to 20 carbon atoms; and n is an integer from 1 to 6.
24. The fuel composition according to claim 23, wherein the additive is present in an amount of from 100 to 5000 ppm based on the fuel composition.
25. The fuel composition according to claim 23, wherein the fuel is selected from the group consisting of gasoline, diesel fuel, fuel oil, heavy oil, kerosene, petroleum, and biofuels such as biodiesel.
26. The additive according to claim 18, wherein the antioxidant is selected from the group consisting of phenols, benzotriazoles, phenylenediamines and diarylamines.
27. The additive according to claim 18, wherein the antioxidant is selected from the group consisting of butylhydroxytoluene (BHT, 2,6-di-tert-butyl-4-cresol), bis(2-ethylhexyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, Bis(2-ethylhexyl) [(4-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, Bis(2-ethylhexyl) [(5-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, Bis(2-ethylhexyl) [(5-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, Bis(2-ethylhexyl) [(6-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, styrenated diphenylamine, and combinations thereof.
28. The additive according to claim 16, wherein the additive further comprises at least one benzotriazole.
29. The additive according to claim 19, wherein the agent for increasing the ignitability is selected from the group consisting of alkyl nitrates and peroxides.
30. The additive according to claim 19, wherein the agent for increasing the ignitability is selected from the group consisting of 2-ethylhexyl nitrate, di-tert-butyl peroxide and combinations thereof.
31. The additive according to claim 20, wherein the solvent comprises at least one polar solvent, in particular an alcohol.
32. The additive according to claim 20, wherein the solvent comprises at least one apolar solvent, in particular a hydrocarbon or a mixture of hydrocarbons.
33. The additive according to claim 16, wherein the additive further comprises at least one benzotriazole, at least one phenol, at least one alkyl nitrate, at least one polar solvent and at least one apolar solvent.
34. The additive according to claim 16, wherein the additive comprises at least 50% by weight of the at least one compound of the general formula (I) and further comprises at least one of the following components: 5 to 10% by weight of one or more phenols and/or 5 to 10% by weight of one or more benzotriazoles; 5 to 10% by weight of one or more alkyl nitrates and/or 5 to 10% by weight of one or more peroxides; 5 to 10% by weight of at least one polar solvent and/or 10 to 20% by weight of at least one apolar solvent.
35. The additive according to claim 16, wherein the additive comprises 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0020]
[0021]
[0022]
[0023]
[0024]
DETAILED DESCRIPTION OF THE DISCLOSURE
[0025] More details of the present disclosure and further embodiments thereof are described below. However, the present disclosure is not limited to the following detailed description, but is merely illustrative of the teachings according to the present disclosure.
[0026] It should be noted that features described in connection with one exemplary embodiment may be combined with any other exemplary embodiment. In particular, features described in connection with an exemplary embodiment of an additive according to the present disclosure may be combined with any other exemplary embodiment of an additive according to the present disclosure, as well as with any exemplary embodiment of a fuel composition according to the present disclosure, as well as any exemplary embodiment of a method according to the present disclosure, as well as any exemplary embodiment of a use according to the present disclosure, and vice versa, unless expressly noted otherwise.
[0027] When a term is denoted by an indefinite or definite article, such as a, an, and the in the singular, this also includes the term in the plural, and vice versa, unless the context clearly specifies otherwise. The expressions comprise or has as used herein not only include the meaning of contain or include, but may also mean consist of and consist essentially of.
[0028] In a first aspect, the present disclosure relates to a bioactive additive (or additive mixture) for a (preferably liquid) fuel.
[0029] The term bioactive as used herein may in particular mean an antimicrobial activity or an antimicrobial efficacy.
[0030] The additive or additive mixture may in particular be a composition, such as a mixture of two, three, four or more components, for addition to a fuel. It may be advantageous if the individual components of the additive form a substantially homogeneous mixture or solution with one another. It may also be advantageous if the additive and the fuel to which the additive is to be added are readily miscible with each other, and in particular form a substantially homogeneous mixture or solution. Even if only an additive is mentioned herein, this may also be understood to mean an additive mixture or a composition for addition to a fuel.
[0031] The additive comprises at least one compound (hereinafter also referred to as imidazoline compound) represented by the general formula (I) given below:
##STR00004##
[0032] In the general formula (I), R represents a saturated or unsaturated hydrocarbon residue having 14 to 20 carbon atoms. The radical R may be a branched or an unbranched hydrocarbon residue, preferably an unbranched (linear) hydrocarbon residue. The radical R may have one or more double bonds, preferably 1 double bond, i.e. a monounsaturated hydrocarbon residue (for example in a cis-configuration or as a Z-isomer). In an embodiment, R is a saturated or unsaturated hydrocarbon residue having 16 to 18 carbon atoms, for example having 17 carbon atoms.
[0033] In the general formula (I), n is an integer from 1 to 6, i.e. the alkyl hydroxy substituent on the imidazoline ring may have from 1 to 6 methylene groups or may be a C1-C6 alkyl hydroxy substituent (branched or unbranched). In an embodiment, n is an integer from 2 to 4, for example 2 or 3, preferably 2.
[0034] According to an exemplary embodiment, the additive (or the at least one imidazoline compound) comprises 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol. This compound has proven to be particularly suitable for use in an additive for a fuel, since it may be used advantageously to achieve a germicidal effect and also an anti-corrosive effect without having toxic or carcinogenic properties.
[0035] According to an exemplary embodiment, the additive contains at least 50% by weight of the at least one compound of the general formula (I), for example from 60 to 90% by weight, and may contain up to 100% by weight of the at least one compound of the general formula (I).
[0036] According to an exemplary embodiment, the additive further comprises at least one antioxidant. In the context of the present application, an antioxidant is understood to mean, in particular, a chemical compound capable of slowing down or (completely) suppressing oxidation of other substances. The addition of an antioxidant may in particular further increase the corrosion-protective effect of the additive.
[0037] Suitable examples of the antioxidant include phenols, benzotriazoles, phenylenediamines, and diarylamines. Among the phenols, sterically hindered phenols, cresols or phenol ethers may be particularly suitable, such as butylated hydroxytoluene (BHT, 2,6-di-tert-butyl-4-cresol) or butylated hydroxyanisole (BHA). Among the benzotriazoles, those functionalized with an amine group, preferably a tertiary amine group, may be particularly suitable, such as bis(2-ethylhexyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, bis(2-ethylhexyl) [(4-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, bis(2-ethylhexyl) [(5-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, bis(2-ethylhexyl) [(5-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, bis(2-ethylhexyl) [(6-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, or a mixture of two or more thereof. Among the diarylamines, styrenated diphenylamine may be particularly suitable.
[0038] According to an exemplary embodiment, the additive contains from 5 to 20% by weight of at least one antioxidant, for example 5 from to 10% by weight of one or more phenols and/or from 5 to 10% by weight of one or more benzotriazoles.
[0039] According to an exemplary embodiment, the additive further comprises at least one agent for increasing the ignitability. In the context of the present application, an agent for increasing the ignitability is understood to mean, in particular, a chemical compound capable of increasing the cetane number of a fuel, in particular a diesel fuel, and accordingly improving its ignitability, so that the fuel ignites itself more easily. Accordingly, the agent for increasing the ignitability may also be referred to as a cetane number improver or cetane number booster.
[0040] Suitable examples of the agent for increasing the ignitability are (organic) peroxides and (organic) nitrates, in particular alkyl nitrates. Among the peroxides, sterically hindered peroxides may be particularly suitable, such as di-tert-butyl peroxide. Among the nitrates, branched or unbranched C6 to C10 alkyl nitrates may be suitable, such as 2-ethylhexyl nitrate.
[0041] According to an exemplary embodiment, the additive contains from 5 to 20% by weight of at least one agent for increasing the ignitability, for example from 5 to 10% by weight of one or more peroxides and/or from 5 to 10% by weight of one or more nitrates.
[0042] According to an exemplary embodiment, the additive further comprises at least one solvent. In the context of the present application, a solvent is understood to mean, in particular, a chemical compound that is capable of dissolving other components, in particular the imidazoline compound, and is also readily miscible with the fuel to which the additive is to be added. The solvent may also provide improved solubility of other components, in particular the imidazoline compound, in the fuel to which the additive is to be added, thus acting as a solubilizer. For this purpose, it may also be advantageous if the solvent comprises a mixture of a (relatively) polar solvent and a (relatively) apolar solvent.
[0043] According to an exemplary embodiment, the solvent comprises at least one polar solvent (or a solvent for increasing polarity) and/or at least one apolar solvent. A suitable example of a polar solvent is an alcohol, such as 2-ethylhexanol, which, moreover, may also increase the ignitability of the fuel and, due to the fact that it may be obtained from renewable raw materials, may have a positive effect on greenhouse gases without a harmful effect on the combustion gases. A suitable example of an apolar solvent is a hydrocarbon or a mixture of hydrocarbons, such as a mixture of C10 to C13 hydrocarbons.
[0044] According to an exemplary embodiment, the additive contains from 5 to 30% by weight of at least one solvent, for example from 5 to 10% by weight of at least one polar solvent and/or from 10 to 20% by weight of at least one apolar solvent.
[0045] According to an exemplary embodiment, the additive comprises at least 50% by weight (up to or ad 100% by weight) of the at least one compound of general formula (I) and further comprises at least one (one, two or all three) of the following components: [0046] 5 to 20% by weight of at least one antioxidant, for example 5 to 10% by weight of one or more phenols and/or 5 to 10% by weight of one or more benzotriazoles; [0047] 5 to 20% by weight of at least one agent for increasing the ignitability, for example 5 to 10% by weight of one or more alkyl nitrates (e.g. 2-ethylhexyl nitrate) and/or 5 to 10% by weight of one or more peroxides (e.g. di-tert-butyl peroxide); [0048] 5 to 30% by weight of at least one solvent, for example 5 to 10% by weight of at least one polar solvent and/or 10 to 20% by weight of at least one apolar solvent.
[0049] According to an exemplary embodiment, the additive or the additive mixture is substantially free from (of) toxic and/or carcinogenic (cancer-causing) compounds. In particular, the additive or the additive mixture may be substantially free from such substances that must be labeled as acutely toxic and/or carcinogenic according to the German Ordinance on Hazardous Substances (GefStoffV). The term substantially free from as used herein means in particular that the additive or the additive mixture contains less than 1% by weight, preferably less than 0.1% by weight, of such compounds and substances.
[0050] In another aspect, the present disclosure relates to the use of an imidazoline compound as described herein as a bioactive additive for a (preferably liquid) fuel.
[0051] According to an exemplary embodiment, the imidazoline compound may be used to reduce the microbial load of the fuel (in particular, to kill germs or prevent microbial infestation). Additionally, the imidazoline compound may also have an anti-corrosive effect.
[0052] In another aspect, the present disclosure relates to the use of an additive as described herein to reduce the microbial load of a fuel (in particular to kill germs) and/or to stabilize a fuel. Additionally, the additive may be used as a corrosion inhibitor.
[0053] The term reducing the microbial load as used herein means, in particular, that the number of (living or active) microorganisms, such as bacteria, viruses, yeasts and fungi, is reduced or microbial infestation is reduced or even avoided. To this end, the additive added to a fuel whose microbial load is to be reduced may have an antimicrobial effect or antimicrobial efficacy.
[0054] In the context of the present application, an antimicrobial effect or an antimicrobial efficacy is understood to mean the ability to kill microorganisms, such as bacteria, viruses, yeasts and fungi, or at least to control or limit their growth. According to an exemplary embodiment, in the context of the present application, an antimicrobial effect or an antimicrobial efficacy is understood to mean an antibacterial and/or antifungal effect or property, and may in particular comprise a bacteriostatic, bactericidal, fungistatic and/or fungicidal effect or property, in particular an efficacy against bacteria, yeasts and/or fungi that may occur or live in fuels.
[0055] According to an exemplary embodiment, the imidazoline compound or additive may be effective against the so-called kerosene fungus (Hormoconis resinae or Amorphotheca resinae). The kerosene fungus is a ubiquitous soil fungus that can degrade kerosene and can also survive in fuel tanks of aircraft, ships and other vehicles. There, its growth can not only cause clogging, but the fatty acids it produces can also lead to corrosion.
[0056] According to an exemplary embodiment, the imidazoline compound or additive may also be effective against other microorganisms causing a so-called diesel bug (bacteria, yeasts, molds), thereby counteracting the formation of biocorrosion and a biosludge in the fuel that may otherwise clog filters and fuel lines.
[0057] In the context of the present application, stabilization of a fuel means the ability to ensure the stability of a fuel over a determined period of time, for example, stability against aging and/or storage stability.
[0058] In the context of the present application, corrosion protection or an anti-corrosive effect is understood to mean the ability to slow down or prevent damage that may be caused to (for example, metallic) components by corrosion, for example, damage to tanks, pipes or other equipment for storing, transporting and/or processing fuels, including damage to an internal combustion engine and its supply lines.
[0059] According to an exemplary embodiment, the fuel is a liquid fuel (at 20? C. and 1 bar). In particular, the fuel may be selected from the group consisting of gasoline (petrol), diesel fuel, fuel oil (heating oil), heavy oil, kerosene, petroleum, and biofuels such as biodiesel.
[0060] In another aspect, the present disclosure relates to a method for reducing microbial load and/or stabilization of a fuel, the method comprising adding an additive as described herein to a fuel. In addition, the method may also provide corrosion protection.
[0061] According to an exemplary embodiment, the additive may already be added to a fuel in the refinery or before storage. Due to its low toxicity, however, the additive may also be added to the fuel by the end user himself as required.
[0062] In another aspect, the present disclosure relates to a fuel composition comprising a (preferably liquid) fuel and an additive as described herein.
[0063] According to an exemplary embodiment, the additive may be present in the fuel composition in an amount of from 100 to 5000 ppm, for example in an amount of from 200 to 4000 ppm, in particular in an amount of from 500 to 2500 ppm, based on the fuel composition. At a proportion of the additive of less than 100 ppm, the antimicrobial and/or stabilization effects may not be achieved in the desired manner. At a proportion of the additive of more than 5000 ppm, it may be that no further increase in the desired antimicrobial and/or stabilization effects is induced.
[0064] In another aspect, the present disclosure relates to a method of operating an internal combustion engine in which a fuel composition as described herein is combusted or used as fuel (or in which method an additive as described herein is added to the fuel).
[0065] According to an exemplary embodiment, the combustion engine is part of a motor vehicle, in particular an automobile (e.g. with gasoline engine or diesel engine, including a hybrid vehicle), a utility vehicle (e.g. a truck or a construction vehicle) or a motorcycle, a ship or an aircraft. In other words, the additive may be added to fuels for all kinds of means of transportation or vehicles. However, the additive may also be added to a fuel for stationary engines or added to a fuel in tanks for fuel storage.
[0066] The additive may be added during the initial filling (so-called first fill) of vehicles, as well as regularly during the entire operating or service life of the vehicle, or even before the vehicle is not used for a longer period of time (for example, in the case of vehicles used only seasonally).
[0067] The present disclosure is further described by reference to the following examples, which, however, serve only to illustrate the teachings of the disclosure and are in no way intended to limit the scope of the present disclosure.
EXAMPLES
First Studies of Antimicrobial Efficacy
Samples Examined:
[0068] TUNAP new: Test solution containing 1% by weight 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol additive (example according to the disclosure). [0069] Standard diesel bug biocide with MBO: test solution containing 0.1% by weight of the biocide MBO (3,3-methylenebis (5-methyloxazolidine)) (comparative sample). [0070] MIT: test solution containing 0.1% by weight of the biocide MIT (2-methyl-2H-isothiazol-3-one), (comparative sample). [0071] Pure fuel: fuel without the addition of an additive (comparative sample)
Tested Microorganisms:
[0072] Hormoconis resinae ATCC 20495 (kerosene fungus) [0073] Yarrowia tropicalis ATCC 48138 (yeast fungus)
[0074] The antimicrobial efficacy of the samples against the tested microorganisms was determined according to DIN EN 15457:2014-11.
[0075] The test results on the efficacy of the tested samples against the tested kerosene fungus are shown in
[0076] The test results on the efficacy of the tested samples against the tested yeast fungus are shown in
Further Studies of Antimicrobial Efficacy
Samples Examined:
[0077] TUNAP active ingredient: test solution containing 1000 ppm 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol additive (example according to the disclosure). [0078] TUNAP Protection System Diesel: test solutions containing 2000 ppm or 5000 ppm of the additive composition 1903391 described below (corresponding to approx. 1000 ppm or 2500 ppm of the active ingredient 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol) (examples according to the disclosure). [0079] Tunap 685 (Protezione Diesel) Biocide with MBO: test solution containing 1000 ppm of the biocide MBO (3,3-methylenebis (5-methyloxazolidine), (comparative sample). [0080] BIT: test solution containing 1000 ppm of the biocide BIT (benzisothiazolinone) (comparative sample). [0081] blank: fuel without addition of an additive (comparative sample)
Additive Composition 1903391:
[0082] at least 50% by weight 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol [0083] 10 to 20% by weight C10-C13 hydrocarbons [0084] 5 to 10% by weight 2,6-di-tert-butyl-4-cresol [0085] 5 to 10% by weight 2-ethylhexanol [0086] 5 to 10% by weight 2-ethylhexyl nitrate [0087] 5 to 10% by weight. of a mixture of bis(2-ethylhexyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, bis(2-ethylhexyl) [(4-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, bis(2-ethylhexyl) [(5-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine, bis(2-ethylhexyl) [(5-methyl-2H-1,2,3-benzotriazol-2-yl)methyl]amine, bis(2-ethylhexyl) [(6-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amine
Tested Microorganisms:
[0088] Hormoconis resinae ATCC 20495 (kerosene fungus) [0089] Pseudomonas aeruginosa DSM 15980 (bacterium) [0090] Yarrowia tropicalis ATCC 48138 (yeast)
[0091] The antimicrobial activity of the samples against the tested microorganisms was determined according to ASTM E 1259-10.
[0092] The test results on the efficacy of the tested samples against the tested kerosene fungus are shown in
[0093] The test results on the efficacy of the tested samples against the tested bacterium are shown in
[0094] The test results on the efficacy of the tested samples against the tested yeast are shown in
[0095] Test solutions with only 250 ppm, 500 ppm and 1000 ppm of the additive composition 1903391, respectively, have also shown very good efficacy against the tested microorganisms (kerosene fungus, bacterium and yeast), which proves the antimicrobial effect of the additive composition over a very wide range of applications.
[0096] The present disclosure has been described with reference to specific embodiments and examples. However, the disclosure is not limited thereto and various modifications thereof are possible without departing from the scope of the present disclosure.